JP2003073468A - Copolycarbonate and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new thermoplastic optical resin excellent in optical characteristics (transparency, high refractive index, high Abbe's number, low birefringence, etc.), good in mechanical and thermal characteristics, excellent in melt flowability and capable of processing by injection molding with good productivity. SOLUTION: This copolycarbonate comprises repeating structural units expressed by formulae (1-a) and (2-a) (where R1 , R2 , R3 and R4 each independently represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom). The optical parts is obtained by molding the copolycarbonate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate copolymer containing a specific repeating unit, a resin composition comprising the copolymer, and an optical component obtained by molding these. The polycarbonate copolymer of the present invention has good transparency, mechanical properties, and thermal properties, and has a relatively high refractive index, low chromatic aberration (high Abbe number), and low birefringence, Further, it has a characteristic that it is rich in melt fluidity and has good moldability, and it is a plastic optical lens such as a spectacle lens for correcting eyesight (spectacle lens), a pickup lens, an optical disk substrate for information recording, a liquid crystal. It is useful as a molding material for various optical components such as plastic substrates for cells, optical fibers and optical waveguides.

[0002]

2. Description of the Related Art Inorganic glass is used in a wide range of fields as a transparent optical material because it has excellent transparency and various physical properties such as small optical anisotropy. However, there are problems that it is heavy and easily damaged, and productivity is poor. In recent years, development of optical resins that replace inorganic glass has been actively carried out. One of the most important properties of optical resins is transparency. To date, polymethylmethacrylate (PM) has been used as an optical resin with good transparency.
MA), bisphenol A polycarbonate (BPA-
PC), polystyrene (PS), methyl methacrylate
-Styrene copolymer (MS), styrene-acrylonitrile copolymer (SAN), poly (4-methyl-1-pentene) (TPX), polycycloolefin (COP), polydiethylene glycol bisallyl carbonate (EGAC), poly Thiourethane (PTU) and the like are known.

PMMA is excellent in transparency and weather resistance and has good moldability, and is widely used as one of typical optical resins. However, the refractive index (nd) is 1.4
It is relatively low at 9 and has the drawback of high water absorption. BPA-PC is excellent in transparency, heat resistance and impact resistance, has a relatively high refractive index (nd = 1.59), and is used in optical applications represented by optical disc substrates for information recording. Since it has drawbacks such as relatively large chromatic aberration (refractive index dispersion) and birefringence, and high melt viscosity and somewhat difficult moldability, its application field as an optical resin is limited. Although PS and MS are excellent in moldability, transparency, low water absorption and high refractivity, they have the drawbacks of being inferior in impact resistance, weather resistance and heat resistance.
Almost no practical use as an optical resin. Also,
SAN is said to have a relatively high refractive index and a good balance of mechanical properties, but its heat resistance is somewhat difficult (heat distortion temperature: 80 to 90 ° C), and it is also used as an optical resin. Absent. TPX and COP have excellent transparency, low water absorption, and heat resistance, but low refractive index (nd = 1.47 to 1.5).
It is also 3) and has the problem of poor impact resistance, gas barrier property and dyeability. EGAC is a thermosetting resin obtained by polymerizing diethylene glycol bisallyl carbonate, which is a monomer, and is most often used for general-purpose eyeglass lens applications. Although it is characterized by good transparency and heat resistance and extremely small chromatic aberration, it has the drawbacks of low refractive index (nd = 1.50) and slightly inferior impact resistance. PTU is a thermosetting resin obtained by the reaction of a diisocyanate compound and a polythiol compound, and in a high refractive index spectacle lens application,
Currently most used. It is an extremely excellent optical resin having excellent transparency and impact resistance, a high refractive index, and relatively small chromatic aberration. However, a long time (1 to 3 days) is required for the thermopolymerization molding process in the process of manufacturing the spectacle lens, which leaves a problem in terms of productivity.

The bisphenol A polycarbonate (BPA-PC, hereinafter referred to as one of typical optical resins)
A novel polycarbonate-based thermoplastic optical resin has been proposed for the purpose of improving the above-mentioned drawbacks found in general-purpose polycarbonate) and obtaining high-quality optical parts in a short time by injection molding. For example, it is disclosed that a polymer such as an alicyclic polycarbonate copolymer having a repeating structural unit derived from an alicyclic dihydroxy compound has relatively low chromatic aberration (high Abbe number) and low birefringence, Utilization for optical applications has been proposed (for example, JP-A-64-66234, JP-A-1-
No. 223119, JP-A No. 11-228683, etc.). According to these methods, it is possible to mold and process an optical component in a short time using the injection molding method, and the obtained optical component has a high Abbe number, or the birefringence is compared. Although it has characteristics such as low cost, it is difficult to say that it is sufficiently satisfactory in practical use as an optical component. That is, for example, when it is used as a spectacle lens, it has some practical problems such as a slightly low refractive index and insufficient heat resistance.

As described above, conventional optical resins have been used in consideration of their characteristics according to their uses, but at present, they have drawbacks and problems to be overcome. Under such circumstances, it has excellent transparency and optical characteristics (high refractive index, high Abbe number, low birefringence, etc.), mechanical characteristics (eg, impact resistance), thermal characteristics (eg,
At present, there is a strong demand for the development of a novel thermoplastic optical resin which has a good heat distortion temperature and the like and is excellent in melt fluidity.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of conventional optical resins, to improve transparency,
A new heat with excellent optical properties (high refractive index, high Abbe number, low birefringence, etc.), good mechanical properties, thermal properties, and excellent melt flowability and injection molding processability. It is to provide a plastic optical resin.

[0007]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.
That is, the present invention relates to a polycarbonate copolymer containing repeating structural units represented by formula (1-a) (formula 3) and formula (2-a) (formula 4).

[0008]

[Chemical 3]

[0009]

[Chemical 4]

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) Furthermore, a resin composition comprising the polycarbonate copolymer, the copolymer The present invention relates to an optical component obtained by molding a united product or a resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
It is a polycarbonate copolymer containing the repeating structural unit represented by the formula (1-a) and the formula (2-a) of the present invention. The polycarbonate copolymer of the present invention,
As will be described in detail later, a dihydroxy compound represented by the following formula (1) (formula 5) and a dihydroxy compound represented by the following formula (2) (formula 6) are allowed to act on a carbonate precursor to copolymerize And a repeating structural unit represented by formula (1-a) derived from a dihydroxy compound represented by formula (1) and a carbonate precursor, and represented by formula (2) Is a copolymer having both repeating structural units of the repeating structural unit represented by the formula (2-a) derived from a dihydroxy compound and a carbonate precursor as essential repeating structural units, wherein the random copolymer is It may be either an alternating copolymer or a block copolymer.

[0012]

[Chemical 5]

[0013]

[Chemical 6]

(Wherein R1, R2, R3 and R4 are the same as above) In these polycarbonate copolymers, optical properties (refractive index, Abbe number), thermal properties, mechanical properties, molding processability, etc. Considering the balance of various physical properties, formula (1-a)
And the molar ratio of all repeating structural units represented by the formula (2-a) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and further preferably. , 20:80 to 80:20.

When the repeating structural unit represented by the formula (1-a) is less than 5 mol%, the Abbe number is low, and the repeating structural unit represented by the formula (2-a) is less than 5 mol%. In this case, thermal properties (heat resistance, etc.), mechanical properties, etc. may be impaired, and the effects of the present invention cannot be sufficiently exhibited when used as an optical resin.

In the formula (2-a), R1, R2, R3
And R4 are each independently a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom, preferably
Hydrogen atom or alkyl group having 1 to 10 carbon atoms, 1 carbon atom
10 represents an alkoxy group or a halogen atom, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the substituents R1, R2, R3 and R4,
For example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
ert-butyl group, n-pentyl group, isopentyl group,
Examples include n-hexyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, fluorine atom, chlorine atom or bromine atom. . The substituents R1, R2, R3 and R4 are more preferably a hydrogen atom or a methyl group, and R1, R2
A hydrogen atom is particularly preferable as 2, R3 and R4.

Among the repeating repeating structural units represented by the formula (1-a), the following formula (1-a-i) (Chemical formula 7),
The repeating structural unit represented by (1-a-ii) (Formula 8) or the formula (1-a-iii) (Formula 9) is more preferable.

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

Among the repeating structural units represented by the formula (2-a), the following formula (2-a-i) (formula 10) and formula (2-
a-ii) (formula 11) or formula (2-a-iii) (formula 1)
The repeating structural unit represented by 2) is more preferable.

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12] (In the formula, R1, R2, R3 and R4 are the same as above.) The polycarbonate copolymer of the present invention is, as described above, represented by the dihydroxy compound represented by the formula (1) and the formula (2). It is produced by reacting a dihydroxy compound with a carbonate precursor to perform copolymerization.

At this time, the dihydroxy compound represented by the formula (1) and the dihydroxy compound represented by the formula (2), which are raw material monomers, are known compounds, respectively, and are suitably produced by a known method and industrially used. Is available at. Examples of the dihydroxy compound represented by the formula (1) include tricyclo [5.2.1.0 ^2,6 ] decane-3,8-dimethanol and tricyclo [5.2.1.
Examples thereof include, but are not limited to, 0 ^2,6 ] decane-3,9-dimethanol and tricyclo [5.2.1.0 ^2,6 ] decane-4,8-dimethanol. .

The dihydroxy compound has stereoisomers (cis-form or trans-form) in addition to the positional isomers for the two hydroxymethyl groups bonded to the tricyclo ring as described above, and further has an exo-form or a isomer. end
Although there are o stereoisomers, the dihydroxy compound represented by the formula (1) used in the present invention may be any of these isomers or a mixture of these structural isomers. It doesn't matter.

Examples of the dihydroxy compound represented by the formula (2) include 1,1-bis (4'-hydroxyphenyl) -1-phenylethane and 1,1-bis (2 ').
-Hydroxyphenyl) -1-phenylethane, 1-
(2′-hydroxyphenyl) -1- (4 ″ -hydroxyphenyl) -1-phenylethane, 1,1-bis (3′-chloro-4′-hydroxyphenyl) -1-phenylethane, 1,1 -Bis (3 ', 5'-dichloro-
4'-hydroxyphenyl) -1-phenylethane,
1,1-bis (3'-bromo-4'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3 ', 5'
-Dibromo-4'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3 ', 5'- Dimethyl-4'-hydroxyphenyl)
-1-phenylethane, 1,1-bis (3'-methoxy-4'-hydroxyphenyl) -1-phenylethane,
1,1-bis (3 ′, 5′-dimethoxy-4′-hydroxyphenyl) -1-phenylethane, 1,1-bis (3′-chloro-2′-hydroxyphenyl) -1-phenylethane, 1 , 1-bis (3 ', 5'-dichloro-
2'-hydroxyphenyl) -1-phenylethane,
1,1-bis (3'-bromo-2'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3 ', 5'
-Dibromo-2'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3'-methyl-2'-hydroxyphenyl) -1-phenylethane, 1,1-bis (3 ', 5'- Dimethyl-2'-hydroxyphenyl)
-1-phenylethane, 1,1-bis (3'-methoxy-2'-hydroxyphenyl) -1-phenylethane,
1,1-bis (3 ′, 5′-dimethoxy-2′-hydroxyphenyl) -1-phenylethane, 1- (3′-chloro-4′-hydroxyphenyl) -1- (3 ″ -chloro- 2 ″ -hydroxyphenyl) -1-phenylethane, 1- (3′5 ′,-dichloro-4′-hydroxyphenyl) -1- (3 ″ 5 ″,-dichloro-2 ″
-Hydroxyphenyl) -1-phenylethane, 1-
(3'-Bromo-4'-hydroxyphenyl) -1-
(3 ″ -bromo-2 ″ -hydroxyphenyl) -1
-Phenylethane, 1- (3'5 ',-dibromo-4'
-Hydroxyphenyl) -1- (3 "5",-dibromo-2 "-hydroxyphenyl) -1-phenylethane, 1- (3'-methyl-4'-hydroxyphenyl) -1- (3 '' -Methyl-2 ''-hydroxyphenyl) -1-phenylethane, 1- (3'5 ',-dimethyl-4'-hydroxyphenyl) -1- (3''
5 ",-dimethyl-2" -hydroxyphenyl)-
1-phenylethane, 1- (3′-methoxy-4′-hydroxyphenyl) -1- (3 ″ -methoxy-2 ″
-Hydroxyphenyl) -1-phenylethane, 1-
Examples thereof include (3′5 ′,-dimethoxy-4′-hydroxyphenyl) -1- (3 ″ 5 ″,-dimethoxy-2 ″ -hydroxyphenyl) -1-phenylethane. It is not limited. In the present invention, the dihydroxy compound represented by the formula (2) may be used alone or in combination of two or more (two or more kinds),
Alternatively, it may be a mixture of these plural compounds.

As the method for producing the polycarbonate copolymer of the present invention, various known polycarbonate polymerization methods [for example, Experimental Chemistry Lecture 4th Edition, (28) Polymer Synthesis,
231 to 242, Maruzen Shuppan (1988), for example, a solution polymerization method, a transesterification method or an interfacial polymerization method] is used. Typically, a dihydroxy compound represented by the formula (1) and a dihydroxy compound represented by the formula (2) are added to a carbonate precursor (for example, a carbonic acid diester compound such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, phosgene, etc. A carbonyl halide compound etc.) is used in the presence of an acid or a base, if necessary.

The molecular weight of the polycarbonate copolymer of the present invention is not particularly limited, but usually G
PC (gel permeation chromatography)
The weight average molecular weight is 5,000 to 200,000, preferably 10,000 to 150,000, and more preferably 30,000 to 120,000 as the standard polystyrene-equivalent molecular weight measured by. The polydispersity index represented as the ratio of the weight average molecular weight and the number average molecular weight is not particularly limited, but is preferably 1.5 to 20.0, and more preferably
2.0 to 15.0, and more preferably 2.0 to
It is 12.0.

The glass transition temperature of the polycarbonate copolymer of the present invention is preferably 80 ° C. or higher for use in various optical parts. On the other hand, if the glass transition temperature is too high, it is not preferable in terms of moldability. That is, the melt flow start temperature and the melt viscosity become relatively high, which makes it difficult to perform molding processing, and causes problems such as poor dyeability when used as a lens for vision correction. The glass transition temperature of the polycarbonate copolymer of the present invention is preferably 90 ° C to 200 ° C.
C., more preferably 100 to 180.degree. C., and even more preferably 100 to 170.degree.

The polycarbonate copolymer of the present invention is a repeating structural unit represented by the formula (1-a) or the formula (2-a) and has a plurality of structures (two or more kinds).
It may contain a repeating structural unit of. Further, the polycarbonate copolymer of the present invention has the formula (1-a) or the formula (2-) as long as the desired effects of the present invention are not impaired.
It may contain a repeating structural unit other than the repeating structural unit represented by a). As the repeating structural unit other than the repeating structural unit represented by the formula (1-a) or the formula (2-a), a dihydroxy group represented by the formula (1) or the general formula (2) is typically used. It is a repeating structural unit derived from a dihydroxy compound other than the compound, and examples of such a dihydroxy compound include various known aromatic dihydroxy compounds or aliphatic dihydroxy compounds.

Specific examples of the aromatic dihydroxy compound include, for example, bis (4-hydroxyphenyl) methane,
1,1-bis (4'-hydroxyphenyl) ethane, 1,2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4 -Hydroxyphenyl) -1-naphthylmethane, 2- (4'-hydroxyphenyl)
-2- (3'-hydroxyphenyl) propane, 2,2-bis (4 '
-Hydroxyphenyl) butane, 1,1-bis (4'-hydroxyphenyl) butane, 2,2-bis (4'-hydroxyphenyl) -3-methylbutane, 2,2-bis (4'-hydroxyphenyl) pentane , 3,3-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) hexane,
2,2-bis (4'-hydroxyphenyl) octane, 2,2-bis
(4'-hydroxyphenyl) -4-methylpentane, 2,2-bis
(4'-hydroxyphenyl) heptane, 4,4-bis (4'-hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl) tridecane, 2,2-bis (4'-hydroxyphenyl) octane , 2,2-bis (3'-methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n- Propyl-4'-hydroxyphenyl) propane, 2,2-bis (3 '
-Isopropyl-4'-hydroxyphenyl) propane,
2,2-bis (3'-sec-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-tert-butyl-4'-
Hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-allyl-4'-hydroxyphenyl) propane,
2,2-bis (3'-methoxy-4'-hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, 2,2-bis (2', 3 ', 5', 6'-tetramethyl-4'-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-tetrachloro-4-hydroxyphenyl) propane, 2,2
-Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (2,3,5,6-)
Tetrabromo-4-hydroxyphenyl) propane, 2
-(3-chloro-4-hydroxyphenyl) propane,
Bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4'-hydroxyphenyl) butane, 2,2-
Bis (hydroxyaryl) alkanes such as bis (4′-hydroxyphenyl) hexafluoropropane;

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 1,1 -Bis (3'-methyl-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dimethyl-
4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) -4- Methylcyclohexane, 1,1-bis (4'-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,
2-bis (4'-hydroxyphenyl) norbornane, 2,2-
Bis (hydroxyaryl) cycloalkanes such as bis (4'-hydroxyphenyl) adamantane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
-Bis (hydroxyaryl) ethers such as dimethyldiphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether; 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3 , 3'-dicyclohexyl-4,
Bis (hydroxyaryl) sulfides such as 4'-dihydroxydiphenyl sulfide and 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4, Four'
-Bis (hydroxyaryl) sulfoxides such as dihydroxydiphenyl sulfoxide, bis (hydroxyaryl) such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone
Sulfones, bis (4-hydroxyphenyl) ketone,
Bis (hydroxyaryl) ketones such as bis (4-hydroxy-3-methylphenyl) ketone;
7'-dihydroxy-3,3 ', 4,4'-tetrahydro-4,4,4',
4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran), trans-2,3-bis (4'-hydroxyphenyl) -2-butene, 9,9-bis (4'-hydroxyphenyl) )
Fluorene, 3,3-bis (4'-hydroxyphenyl) -2-
Butanone, 1,6-bis (4'-hydroxyphenyl) -1,6-
Hexanedione, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin and the like can be mentioned.

Specific examples of the aliphatic dihydroxy compound include 1,2-dihydroxyethane, 1,3-dihydroxypropane, 1,4-dihydroxybutane and 1,5-
Dihydroxypentane, 3-methyl-1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7
-Dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,
12-dihydroxydodecane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-
Chain-like aliphatic dihydroxy compounds such as methyl-1,3-dihydroxypropane; Cyclic aliphatic dihydroxy compounds such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol;
o-dihydroxyxylylene, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis (2'-hydroxyethyl) benzene, 1,4-bis (3'-hydroxypropyl) benzene, 1,4- Bis (4′-hydroxybutyl) benzene, 1,4-bis (5′-hydroxypentyl) benzene, 1,4-bis (6′-hydroxyhexyl) benzene, 2,2-bis [4 ′-(2 ″) -Hydroxyethyloxy) phenyl]
Examples thereof include aliphatic dihydroxy compounds containing an aromatic group such as propane, but the present invention is not limited thereto.

Further, the formula (1-a) or the formula (2-a)
As the repeating structural unit other than the repeating structural unit represented by, a repeating structural unit derived from a bifunctional compound other than the above dihydroxy compound may be contained. That is, examples of the bifunctional compound other than the dihydroxy compound include compounds such as aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diamines, aliphatic diamines, aromatic diisocyanates, and aliphatic diisocyanates. By using these bifunctional compounds, a polycarbonate copolymer containing a group such as an imino group, an ester group, an ether group, an imide group, an amide group, a urethane group and a urea group in addition to a carbonate group is obtained, The present invention also includes such a polycarbonate copolymer.

When a repeating structural unit other than the repeating structural unit represented by the formula (1-a) or the formula (2-a) is contained, the formula (1-
The proportion of the repeating structural units represented by a) and formula (2-a) is not particularly limited as long as it does not impair the desired effects of the present invention, but is usually 50 mol% or more. And preferably 70 mol% or more,
It is more preferably 80 mol% or more, and further preferably 90 mol% or more. In order to obtain the maximum effect of the present invention, it contains only the repeating structural unit represented by the formula (1-a) and the formula (2-a) without containing other repeating structural units. Is particularly preferred.

In the polycarbonate copolymer of the present invention, the terminal group may be a reactive terminal group such as a hydroxy group, a haloformate group and a carbonic acid ester group.
It may be an inert terminal group sealed with a molecular weight regulator. The amount of the terminal group in the polycarbonate copolymer of the present invention is not particularly limited, but is usually 0.001 to 10 mol% based on the total number of moles of the structural unit, and preferably,
0.01 to 5 mol%, more preferably 0.05
˜3 mol%, and more preferably 0.1 to 2 mol%. When the polycarbonate copolymer of the present invention is polymerized and produced according to the above method, it is preferable to carry out the polymerization in the presence of a molecular weight regulator (terminal blocking agent) for the purpose of controlling the molecular weight.

The molecular weight modifier is not particularly limited, and may be any known molecular weight modifier used in known polycarbonate polymerization, for example, a monovalent hydroxy aliphatic compound or hydroxy aroma. Group compounds or derivatives thereof (for example, monovalent hydroxyaliphatic compounds or alkali metal or alkaline earth metal salts of hydroxyaromatic compounds, monovalent hydroxyaliphatic compounds or haloformate compounds of hydroxyaromatic compounds, monovalent hydroxy compounds) Carbonic acid esters of aliphatic compounds or hydroxyaromatic compounds), monovalent carboxylic acids or derivatives thereof (for example, alkali metal or alkaline earth metal salts of monovalent carboxylic acids, acid halides of monovalent carboxylic acids, 1 Carboxylic acid esters, etc.) and the like. The amount of the molecular weight modifier used is not particularly limited and may be used as desired to adjust the molecular weight to a desired value, but is usually 0.001 to 10 with respect to the total number of moles of the dihydroxy compound to be polymerized. Mol%, preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%, and further preferably
It is 0.1 to 2 mol%.

The polycarbonate copolymer of the present invention has various known additives such as antioxidants (for example, phosphorus atom-containing compounds, at the time of production or molding) as long as the desired effects of the present invention are not impaired. Phenolic compounds, hindered phenolic compounds, sulfur atom-containing compounds, etc.), ultraviolet absorbers, mold release agents (eg higher fatty acid esters of monohydric or polyhydric alcohols), lubricants,
Flame retardants (eg organic halogen compounds), dyes,
A fluidity improver, a heat stabilizer (for example, a sulfur atom-containing compound, etc.) and the like may be added together and used. Further, the polycarbonate copolymer of the present invention, for example, an antistatic agent,
Fillers (for example, calcium carbonate, clay, silica, glass fibers, glass beads, carbon fibers, etc.) may be added and used as various molding materials other than optical parts.

The polycarbonate copolymer of the present invention can be used as a molding material by mixing with other polymers at the time of production or molding so long as the desired effects of the present invention are not impaired. Other polymers include polyethylene, polypropylene, polystyrene, ABS resin,
Polymethylmethacrylate, polytrifluoroethylene,
Polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyamide, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, paraoxybenzoyl-based poly (thio) ester, polyarylate, polysulfide Etc.

The resin composition comprising the polycarbonate copolymer of the present invention comprises the polycarbonate copolymer of the present invention as an essential component and other components such as antioxidants (for example, phosphorus atom-containing compounds, phenolic compounds, hinders). Dephenol compounds, sulfur atom-containing compounds, etc.)
And the like. The amount of the antioxidant added to the resin composition of the present invention is usually 0.0001 with respect to 100 parts by weight of the polycarbonate copolymer of the present invention.
10 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.05 to 3 parts by weight.

Examples of such antioxidants include trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, tris (2-ethylhexylphosphite), trinonylphosphite, tridecylphosphite, tris (phosphite). Tridecyl) phosphite, trioctadecyl phosphite, tristearyl phosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl phosphite), tricyclohexyl phosphite, triphenyl phosphite, tricresyl phosphite Fight,
Tris (ethylphenyl) phosphite, Tris (2,
4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, phenyl-didecylphosphite, diphenyl-isooctylphosphite, diphenyl-2-ethylhexylphosphite, diphenyl-decylphosphite, diphenyl- Tridecyl phosphite, bis (tridecyl) -pentaerythyryl-diphosphite, distearyl-pentaerythyryl-diphosphite, diphenyl-pentaerythyryl-diphosphite, bis (nonylphenyl) -pentaerythyryl-diphosphite, bis (2,4) -Ge-t
ert-Butylphenyl) -pentaerythyryl-diphosphite, bis (2,6-di-tert-butyl-4)
-Methylphenyl) -pentaerystyryl-diphosphite, tetraphenyl-dipropyleneglycol-diphosphite, tetra (tridecyl) -4,4'-isopropylidenediphenyl-diphosphite, tetra (2,2
Phosphorous acids such as 4-di-tert-butylphenyl) -4,4′-diphenylphosphite, tetraphenyltetra (tridecyl) pentaerystyryltetraphosphite, trilauryltrithiophosphite;

Trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diphenyl mono-orthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate,
Phosphoric acids such as diisopropyl phosphate; tetrakis (2,4-di-tert-butylphenyl) -4,4
-Phosphonous acids such as diphenylene phosphonite; phosphorus atom-containing compounds such as dimethyl benzenephosphonate, diethyl benzenephosphonate, phosphonic acids such as diisopropyl benzenephosphonate, octadecyl-3-
(3,5-di-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1 ，
6-hexanediol-bis [3- (3,5-di-te
rt-butyl-5-methyl-4-hydroxyphenyl)
Propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-5-methyl-
4-hydroxyphenyl) propionate], 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
ert-butyl-4-hydroxybenzyl) benzene,
N, N-hexamethylenebis (3,5-di-tert-
Butyl-4-hydroxy-hydrocinnamide), 3,
5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (3,5-di-t
Known phenolic compounds such as ert-butyl-4-hydroxybenzyl) isocyanurate are exemplified, but the invention is not limited thereto. These antioxidants may be used alone or in combination of two or more kinds.

In addition to the antioxidant, the above-mentioned ultraviolet absorbers and mold release agents (for example, higher fatty acid esters of monohydric or polyhydric alcohols, etc.) may be used as long as the desired effects of the present invention are not impaired. ), A lubricant, a flame retardant (for example, an organic halogen compound), a dye, a fluidity improver, and a heat stabilizer (for example, a sulfur atom-containing compound).

Further, the resin composition of the present invention may optionally contain higher fatty acid esters of monohydric or polyhydric alcohols for the purpose of improving mold releasability from the mold during melt molding. It is preferable. The higher fatty acid esters added to the resin composition of the present invention are added in an amount of 100 parts by weight of the polycarbonate copolymer of the present invention.
Usually, it is 0.0001 to 2 parts by weight, and preferably,
0.001 to 1 part by weight, more preferably 0.0
1 to 0.5 parts by weight.

The higher fatty acid esters are more preferably partial esters or total esters of monohydric or polyhydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Specific examples of the higher fatty acid esters include stearic acid monoglyceride, stearic acid monosorbate, behinic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol monostearate, and steryl stearate. Examples thereof include, but are not limited to, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate and the like. These higher fatty acid esters may be used alone or in combination of two or more.

The method for producing the resin composition of the present invention is not particularly limited, and generally, various known methods for producing the resin composition can be used. That is, (1)
A method of isolating the polycarbonate as a solid after adding the above-mentioned antioxidant to the solution or the molten polycarbonate, (2) isolating the polycarbonate as a solid from the solution or the molten polycarbonate, and then adding the solid to the solid On the other hand, the above-mentioned antioxidant is added, and various known mixing devices (eg, tumbler mixer, V
Type blender, Nauter mixer, Henschel mixer, ribbon blender, super mixer, etc.), or (3) As described above, after dispersion mixing with various mixers, with an extruder, Banbury mixer, roll, etc. Examples thereof include a method of melt kneading.
Further, these methods may be used in combination. The polycarbonate copolymer of the present invention or the resin composition containing the copolymer is thermoplastic, and in a molten state, injection molding, extrusion molding, blow molding, injection compression molding, further, such as solution casting. It is suitably molded by various known molding methods.

The molding method for molding the polycarbonate copolymer of the present invention or the resin composition containing the copolymer to obtain an optical component is preferably injection molding, extrusion molding or injection compression molding. Yes, and more preferably injection molding or injection compression molding. Molding conditions for molding an optical component by molding the polycarbonate copolymer or resin composition of the present invention, it can be performed under any conditions depending on the thermal characteristics of the resin or resin composition, usually, the resin temperature 180-350 ℃, mold temperature 25 (room temperature)
To 160 ° C., preferably a resin temperature of 180
˜300 ° C., mold temperature 50 to 150 ° C., more preferably resin temperature 180 to 300 ° C., mold temperature 50 to 150 ° C. The polycarbonate copolymer of the present invention has excellent transparency and optical characteristics (high refractive index, high Abbe's number, low birefringence, etc.), good thermal characteristics, mechanical characteristics, and moldability. Since it has good productivity, it is useful as a material for various optical components.

The optical parts of the present invention include spectacle lenses for vision correction, lenses for image pickup devices (for example, cameras, VTRs, etc.), pickup lenses, collimation lenses,
Various optical components such as various plastic optical lenses such as fΘ lens and Fresnel lens, optical recording medium substrates such as optical disc substrates and magneto-optical disc substrates, plastic substrates for liquid crystal cells, optical fibers and optical waveguides can be mentioned. Further, the polycarbonate copolymer of the present invention or a resin composition containing the copolymer is used as a molding material for applications other than the above-mentioned optical parts, for example, electric equipment, electronic parts, vehicle parts, building materials, etc. It can also be used. The optical component of the present invention obtained by the above method is excellent in transparency and optical properties (high refractive index, high Abbe number, low birefringence index, etc.), thermal properties, mechanical properties, etc.,
It is preferably used in the applications as exemplified above.

[0050]

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Physical properties of the polycarbonate copolymers produced in the following examples and the resin compositions containing the polycarbonate copolymers were measured by the following methods. [Measurement of weight average molecular weight] A 0.2% by weight chloroform solution of the polycarbonate copolymer produced in the following examples was used as a GPC (gel permeation chromatography) [Showa Denko KK, System-1
1] to determine the weight average molecular weight (Mw).
The measured values are values converted into standard polystyrene. [Melt flow start temperature and melt viscosity] Shimadzu Koka type flow tester (CFT500A) is used, and the load is 100 kg.
Was measured using an orifice having a diameter of 0.1 cm and a length of 1 cm. [Refractive index, Abbe number] The obtained polycarbonate copolymer was press-molded by a press at 240 ° C to prepare a sheet-shaped test piece, and the refractive index (nd) and Abbe number at 20 ° C were measured using a Pulfrich refractometer. (Νd) was determined. [Birefringence] A 5 μm thick thin film of the polycarbonate copolymer produced in the example was formed on a silicon wafer.
That is, 1,1,1-of the polycarbonate copolymer
The trichloroethane solution (20% concentration) was filtered through a Teflon (registered trademark) filter (pore diameter 0.45 μm), and then rotated on a silicon wafer (diameter 5 inches) at a rotation speed of 20.
Spin coating was performed under the conditions of 00 rpm and 5 seconds. Then, it was dried at 70 ° C. for 15 minutes to distill off the solvent to form a polycarbonate thin film having a thickness of 5 μm. 63 using a prism coupler (Metricon model 2020)
With a 2 nm laser light source, TE mode light and T
The refractive index with M-mode light was measured, and the birefringence was calculated as the difference between them.

Example 1 [Production of Polycarbonate Copolymer of the Present Invention and Measurement of Physical Properties] Tricyclo [5] was placed in a flask having an internal volume of 2 liters equipped with a stirrer, a reflux condenser, a thermometer, and a dipping tube for blowing carbonyl chloride. 2.2.1.0 ^2,6 ] decanedimethanol 4
9.07 g (0.25 mol), 1,1-bis (4'-hydroxyphenyl) -1-phenylethane 72.59
g (0.25 mol), phenol 235 mg (0.0
025 mol; 0.5 mol% with respect to the total dihydroxy compound), pyridine 199 g (2.5 mol) and dichloromethane 450 g were weighed and under a nitrogen atmosphere at 10 ° C.
It was dissolved by stirring (under ice-water cooling). 59.4 g of carbonyl chloride was added to this mixed solution through an immersion tube.
(0.60 mol) was blown in at the same temperature for 6 hours. After the completion of blowing, the mixture was further stirred at the same temperature for 1 hour, and the reaction solution was analyzed by GPC. As a result, the weight average molecular weight was 6.3 × 10 ⁴ . 10 to the reaction solution
% Hydrochloric acid (1000 g) was added dropwise at 15 ° C. (under ice-water cooling) over 3 hours, the layers were separated, the organic layer was taken out, and the organic layer was washed with water and the layers were separated again. The resulting organic layer (dichloromethane solution) was added dropwise to 4000 g of vigorously stirred methanol over 2 hours, and the precipitated solid was collected by filtration and washed thoroughly with 1000 g of methanol. After drying at 60 ° C. for 20 hours under reduced pressure, 129.3 g (yield 96%) of the desired polycarbonate copolymer was obtained as a white powdery solid. The obtained polycarbonate copolymer had a weight average molecular weight of 6.2 × 10 ⁴ in terms of standard polystyrene in GPC analysis. The results of ¹ H-NMR (270 MHz) measurement of a 1 wt% deuterated chloroform solution of the obtained polycarbonate copolymer are shown below. ¹ H-NMR δ (CDCl ₃ ): 0.99 to 1.11
(M, 1H), 1.30 to 1.72 (m, 8H), 1.
95-2.30 (m, 7H), 2.40-2.60
(M, 1H), 3.89 to 4.21 (m, 4H), 7.
08 to 7.29 (m, 13H) From the result of the ¹ H-NMR measurement, the formula (1-a-1)
The hydrogen (3.89 to 4.21 ppm) of the oxymethylene group in the repeating structural unit represented by the formula
-A-1) Hydrogen of the aromatic ring represented by Chemical formula 14 (7.0)
8 to 7.29 ppm)
The molar ratio of the repeating structural unit represented by the following formula (1-a-1) and the repeating structural unit represented by the following formula (2-a-1) contained in the obtained polycarbonate copolymer is , 50:50 was confirmed.

[0052]

[Chemical 13]

[0053]

[Chemical 14]

When the physical properties of the obtained polycarbonate copolymer of the present invention were measured according to the above-mentioned method, the glass transition temperature (Tg) was 128 ° C. Melt flow start temperature is 180 ° C, melt viscosity is 230 ° C, 760 Pa
s (7600 poise). Refractive index (nd) 1.5
The Abbe number was 80 and the Abbe number (νd) was 36, which was higher than that of general-purpose polycarbonate. The birefringence is 9
The value was × 10 ⁻⁴ , which was lower than that of a general-purpose polycarbonate.

Example 2 A flask having an internal volume of 2 liters equipped with a stirrer, a reflux condenser, a thermometer, and a dipping tube for blowing carbonyl chloride was charged with tricyclo [5.2.1.0 ^2,6 ] decanedimethanol 5
8.89 g (0.3 mol), 1,1-bis (4'-hydroxyphenyl) -1-phenylethane 58.07 g
(0.2 mol), phenol 235 mg (0.002
5 mol; 0.5 mol% with respect to all dihydroxy compounds), pyridine 199 g (2.5 mol) and dichloromethane 450 g were weighed and dissolved by stirring at 10 ° C. (under ice water cooling) in a nitrogen atmosphere. It was 59.4 g of carbonyl chloride was added to this mixed solution through an immersion tube.
(0.60 mol) was blown in at the same temperature for 5 hours. After the completion of blowing, the mixture was further stirred at the same temperature for 1 hour, and the reaction solution was analyzed by GPC. As a result, the weight average molecular weight was 6.9 × 10 ⁴ . 1 to the reaction solution
After 1000 g of 0% hydrochloric acid was added dropwise at 15 ° C. (under ice-water cooling) over 2 hours, the layers were separated, the organic layer was taken out, washed with water until the aqueous layer became neutral, and the layers were separated. The resulting organic layer (dichloromethane solution) was added dropwise to 4000 g of vigorously stirred methanol over 2 hours, and the precipitated solid was collected by filtration and washed thoroughly with 1000 g of methanol. After drying at 60 ° C. for 20 hours under reduced pressure, 123.45 g (yield 95%) of the desired polycarbonate copolymer was obtained as a white powdery solid. The obtained polycarbonate copolymer had a weight average molecular weight of 6.87 × 10 ⁴ in terms of standard polystyrene by GPC analysis, and 1H.
A repeating structural unit represented by the above formula (1-a-1) and a repeating structural unit represented by the following formula (2-a-2) in the polycarbonate copolymer obtained from the results of NMR measurement; The molar ratio was 60:40. Physical properties of the obtained polycarbonate copolymer of the present invention were measured according to the above method, and the glass transition temperature (Tg) was 117 ° C. The melt flow starting temperature is 175 ° C and the melt viscosity is 2
It was 650 Pa · s (6500 poise) at 30 ° C.
The refractive index (nd) was 1.575 and the Abbe number (νd) was 37, which was a high Abbe number as compared with general-purpose polycarbonate. The birefringence was 10 × 10 ⁻⁴ , which was lower than that of general-purpose polycarbonate.

Comparative Example 1 (Measurement of Physical Properties Using Known Polymethyl Methacrylate and Manufacture of Optical Parts) Physical properties were measured by using the known polymethylmethacrylate resin (general optical grade) according to the above method.
The glass transition temperature (Tg) is 111 ° C., and the refractive index (n
d) 1.487, an Abbe number (νd) 54, birefringence 1 × 10 ^- was ⁴ or less.

Comparative Example 2 (Measurement of Physical Properties Using Known General Purpose Polycarbonate) Using a known general purpose polycarbonate (optical disk grade; weight average molecular weight of 30,000), according to the method described above.
Physical properties were measured. Glass transition temperature (Tg) is 130 ° C
And the refractive index (nd) is 1.580 and the Abbe number (νd) is
It was 30. The birefringence was 70 × 10 ⁻⁴ .

Comparative Example 3 (Measurement of Physical Properties Using Polycarbonate Described in Japanese Patent Laid-Open No. 64-22632) According to the same method as that described in Example 2 of Japanese Laid-Open Patent Publication No. 64-22632, polycarbonate (tricyclo The molar ratio of the repeating structural unit of the polycarbonate derived from [5.2.1.0 ^2,6 ] decane dimethanol to the repeating structural unit of the polycarbonate derived from bisphenol A was 25:75). Then, the physical properties were measured according to the methods described above. Glass transition temperature (T
g) The temperature was 131 ° C., the refractive index (nd) was 1.572, and the Abbe number (νd) was 34. The birefringence was 55 × 10 ⁻⁴ .

Example 3 [Production of molding material for optical parts of the present invention comprising poly (thio) ester copolymer obtained in Example 1] 100 parts by weight of the polycarbonate copolymer produced in Example 1, Tris 0.1 part by weight of (2,4-di-tert-butylphenyl) phosphite and 0.1 part by weight of pentaerystyryl [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] are added. , Mixed with a Henschel mixer, then a single screw extruder (65m
m) was melt-kneaded while being degassed at a cylinder temperature of 210 ° C., and extruded into pellets to obtain a colorless transparent pellet-shaped resin composition.

Example 4 [Manufacture of Optical Component of the Present Invention] A lens-shaped molded product was manufactured by injection molding using the resin composition obtained in Example 3 above. That is, after drying the pellets of the resin composition under reduced pressure at 80 ° C. for 24 hours,
Injection molding with a 30t direct pressure molding machine at a molding temperature of 230 ° C and a mold temperature of 80 ° C, colorless and transparent, plus lens (convex lens; diameter 75mm, center thickness 4.2mm, edge thickness 1.0)
mm, +2.00 D) shaped molded body was obtained. When this molded product was observed between polarizing plates, striae, distortion, etc. were not observed, and it was low in birefringence and optically uniform. As described above, by using the molding material of the present invention, the temperature (230
It was possible to produce a molded product which was capable of being molded at (° C.) and was optically homogeneous. Further, the plastic lens of the present invention thus obtained has various physical properties such as transparency, mechanical characteristics (impact resistance, tensile strength, bending strength, etc.), thermal characteristics (heat deformation temperature, etc.), light resistance, etc. In practice, it showed good characteristics.

[0061]

The polycarbonate copolymer of the present invention is
Excellent optical properties (transparency, high refractive index, high Abbe number, low birefringence, etc.), good mechanical properties, thermal properties, excellent melt flowability, and good productivity From
It is very useful as a molding material for various optical parts. The optical component of the present invention obtained by the above method has excellent optical characteristics (transparency, high refractive index, high Abbe number, low birefringence index, etc.),
It has excellent mechanical and thermal properties and is extremely useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 69:00 G02B 6/12 N (72) Inventor Atsuo Otsuji 580, Nagaura, Sodegaura, Chiba 32 Mitsui In-house F-term (reference) 2H047 KA02 PA02 QA02 2H050 AA13 AA15 AB50Z 4F071 AA50 AF13 AF30 AF31 AF43 AH19 BA01 BB05 BC07 4J029 AA09 AB01 AB07 AC02 AD01 AD05 AD07 AE04 BB12 BD10 HC01 HC04 HC05

Claims (4)

[Claims] 1. A formula (1-a) (Formula 1) and a formula (2-a)
A polycarbonate copolymer containing a repeating structural unit represented by (Chemical Formula 2). [Chemical 1] [Chemical 2] (In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom) 2. A resin composition comprising the polycarbonate copolymer according to claim 1. 3. An optical component obtained by molding the polycarbonate copolymer according to claim 1. 4. An optical component obtained by molding the resin composition according to claim 2.